text:
|Publication number
|Publication type
|Application number
|Publication date
|Jul 27, 1999
|Filing date
|Apr 3, 1997
|Priority date
|Apr 3, 1997
|Fee status
|Also published as
|Publication number
|Terri L. Butler, Kathryn R. Bretscher, Mark C. Berens, James A. Baker, Gaye K. Lehman
|Original Assignee
|Minnesota Mining And Manufacturing Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (23), Non-Patent Citations (23), Referenced by (34), Classifications (27), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is related to U.S. patent application Ser. No. 08/724,073 by virtue of common assignee, similar subject matter, and some common inventors. This application is also related to copending, concurrently filed, U.S. patent application Ser. Nos. 08/832,543, abandoned 08/832,834, 08/828,823 and 08/832,934, (Attorney Docket Nos. 53268USA5A, 53267USA7A, 53322USA9A, and 52291USA3A, respectively), by virtue of common assignee, similar subject matter, and some common inventors.
This present invention relates to controlling the arrangement of release coatings on surfaces.
International Patent Publication WO 96/23595 (Melancon et al.) discloses a process, referred to as a carrier fluid process, for coating a composite layer onto a web. The composite layer comprises a carrier layer of fluid (such as water) and one or more functional layers (such as silicone or other polymeric materials). With subsequent removal of the carrier fluid layer, only the functional layer is left on the web. The advantage of this process is that it can be used to generate thin (i.e. less than 100 microns) and ultrathin coatings (i.e. less than 1 micron coatings) without solvent dilution.
U.S. Pat. No. 5,061,535 (Kreckel, et al.) discloses the generation of geometric patterns by flexographic or gravure printing.
The coating art also employs "Langmuir-Blodgett" type bath coaters such as described by K. Blodgett in Journal of the American Chemical Society, vol. 57 1935, p. 1007 and U.S. Pat. No. 4,093,757 (Barraud, et al 1978) and Japanese Patent Application 63-327260 (Masutani, etal 1990). In Langmuir bath coating, a functional layer, comprising a coating formulation is floated on the surface of a bath of water or another supportive (carrier) liquid and is then transferred to a substrate or web by dipping or rolling the substrate off of the bath surface.
Traditional methods of applying coatings to minimize coating defects are discussed in Cohen, E. D. and Gutoff, E. B., Modern Coating and Drying Technology, VCH Publishers, New York 1992 and Satas, D., Web Processing and Converting Technology and Equipment, Van Norstrand Reinhold Publishing Co., New York 1984.
The apparatus and method of this invention coats patterned thin to ultra-thin liquid films onto substrates. The invention includes floating or supporting a coating or functional fluid(s) on a carrier fluid, this plurality of fluid layers forming a composite. A substrate and the composite are moved in relative motion to each other so as to effect contact.
Preferably, composite layer and substrate move at a rate relative to each other that is sufficiently high enough to form a continuous fluid bridge of composite layer across the coating width of the substrate.
The contact between the composite layer and substrate results in interposing the coating or functional layer between the substrate and the carrier fluid. The carrier fluid is at least partly removed by mechanical or evaporative means while leaving the coating fluid(s) on the substrate as a coating layer. By appropriate choice of functional layer(s), carrier fluid and coating conditions, consistent patterns can be formed in the functional layer which impart useful features. The functional layer can be cured by thermal or radiative means to generate a crosslinked patterned coating. Miscible and immiscible combinations of coating and carrier fluids may be used in the composite layer.
The invention as described above differs from the fluid carrier coating processes described in Melancon et al (WO 96/23595) which is incorporated herein by reference. As significant an improvement to the coating art that Melancon et al. is, nonetheless Melancon et al. do not specifically address issues related to various coating properties, such as homogeneity, surface coverage, patterning, optical clarity, and the like, important for the coating of release surfaces. The disclosure of the Melancon et al. coating process also does not address the utility of using coating patterns to modulate functional performance, e.g., release performance. Melancon et al. also does not disclose the use of a fluid carrier to generate these patterns.
Also, "Langmuir Blodgett" type coaters have not been used in a manner to generate coating patterns for the purpose of improving functional performance of the resulting coated surface.
In fact, conventional coating literature regards coatings exhibiting such patterns as potentially flawed or defective. Such coating defects are discussed in detail in E. Cohen and E. Gutoff, Modern Coating and Drying Technology (see for example pp. 79-85, 156-163 and 287-290).
One aspect of the present invention is a novel approach for generating, modulating and controlling patterns produced using the Melancon et al. carrier fluid coating process or the "Langmuir Blodgett" bath coating process. The method of making a patterned coating comprises the steps of (a) dispensing a composite comprising a carrier fluid layer and a functional fluid layer; (b) bringing the composite into contact with a substrate; (c) transferring the composite to the substrate, wherein interfacial interaction among the carrier fluid layer, the functional fluid layer, and the substrate generates a patterned coating of the functional layer on the substrate.
Preferably, these coating methods can be used to provide glossy smooth coatings, translucent patterned coatings, or porous coatings.
Another aspect of the present invention is an article comprising a patterned coating on a substrate, prepared according to the above method, wherein the article comprises a temporary electrographic image receptor, a release liner, a low-adhesion-backsize material, a differential release layer, a microporous membrane, an adhesive tape, a high diffusion gradient functional layer, a filter, or a porous substrate surface modifier. The temporary electrographic image receptor can be either an electrophotographic image receptor or an electrostatic image receptor.
Another aspect of the present invention is the use of a fluid carrier in carrier fluid coating and bath coating processes to obtain controlled patterns that have desirable performance properties. Preferably, the coating patterns can comprise either generation or attenuation from a uniform coating thickness previously used in the art.
"Pattern" means an inhomogeneous coating that varies in thickness, spacial resolution, and material composition across and down web in a random, symmetrical, or periodic fashion using any theory of geometry, including without limitation, Euclidian geometry and fractal geometry.
A feature of the present invention is the ability to use known coating techniques in previously unknown manners to control the appearance, surface texture, pattern, and resulting coated surface properties of any substrate so coated.
Another feature of the present invention is the ability to generate patterns in ultra-thin liquid coatings.
Another feature of the present invention is the ability to use silicone-based release compositions in the modulated coating processes in order to provide controlled release surface patterns (on a microscopic or macroscopic scale) for use with a variety of materials that benefit from temporary contact with such patterned controlled release surfaces.
Another feature of the present invention is the ability to apply a variety of processing parameters to control (i.e., random variation, gradual variation, periodic variation, etc.) how a release surface is constructed for further industrial use.
Another feature of the present invention is the ability to generate patterned coatings from 100% solids formulations, i.e. without solvent dilution thereby avoid environmental pollution and other hazards and costs associated therewith.
Another feature of the invention is the ability to generate and control unique patterns without additional machine costs, as one might incur from tooling gravure rolls.
Another feature is the ability to make rough surfaces without tooling or additives.
Another feature is the ability to modulate peel force in tightly crosslinked coatings by varying coating parameters (as opposed to formulation and additives).
An advantage of the present invention is the versatility of using advanced known coating techniques in unexpected ways to accomplish the surprising results of producing release surfaces with precise patterns.
Another advantage of the present invention is the use of patterned release surfaces on temporary image receptors, as disclosed in copending, coassigned U.S. patent application Ser. No. 08/832,834 (Bretscher et al.) (Attorney Docket No. 53267USA5A) and as disclosed in copending, coassigned U.S. patent application Ser. No. 08/832,543, abandoned (Baker et al.) (Attorney Docket No. 53268USA5A).
Further features and advantages of the invention are apparent from a description of embodiments of the invention in conjunction with the following drawings.
FIG. 1 is comprised of FIGS. 1A, 1B, 1C, and 1D and are photomicrographs of coatings of the present invention in an experiment that varies coating thicknesses of 10,600, 5300, 2650, and 1325 Å, respectively, while maintaining constant viscosity of the coating composition.
FIG. 2 is comprised of FIGS. 2A and 2B and are photomicrographs of coatings of the present invention in an experiment that varies viscosities of the coating composition of 500 and 30,000 mPas, respectively, while maintaining constant coating thickness.
Functional Layer Composition
As used in the present invention, nonlimiting examples of functional layers include monomers, oligomers, solutions of dissolved solids, solid-fluid dispersions, fluid mixtures, and emulsions. Such fluids are useful in producing a wide range of functional coatings on webs including release coatings, low adhesion coatings, priming layers, adhesive coatings, protective coatings, optically active coatings, and chemically active coatings.
Coatings made by this invention can have utility in manufacturing products such as release liners, pressure-sensitive tapes, photographic film, electrographic printing media, magnetic recording tapes, gas separation membranes, reflective sheeting and signing, medical dressings, coated abrasives, printing plates, membranes and films. Functional coating fluids may be miscible or immiscible with the carrier fluid. Preferably, the functional fluid layer is selected from the group consisting of a release material, an adhesive, a primer, and a low adhesive backsize material.
Preferred functional layer formulations include silicone-urea release formulations (as disclosed in U.S. Pat. No. 5,045,391 (Brandt et al.) incorporated by reference herein); and silicone or fluorosilicone polymers (such as ethylenically unsaturated-, hydroxy-, epoxy- terminated or pendant functional silicone and fluorosilicone pre-polymers); or other release polymers with suitable low surface energy (such as poly(organosiloxanes), fluoropolymers, and the like) as disclosed copending, coassigned U.S. patent applications Ser. Nos. 08/724073 (Attorney Docket No. 52070USA5A); and 08/832,824 (Attorney Docket No. 53267USA7A), the disclosures of which are incorporated by reference herein. The mole percent of crosslinkable groups is preferably about 0 to 20 mole %, more preferably about 0-15 mole percent, and most preferably about 0-10 mole percent. For addition cure systems, both vinyl and alkenyl (number of carbons greater than 2 and less than 10) crosslinking groups may be used. The distribution of crosslinks may be multimodal, especially in the presence of higher molecular weight silicone gums as additives.
More preferably, functional layers are selected from the group consisting of ethylenically unsaturated-terminated and/or pendant silicone pre-polymers, silicone-urea polymers, and epoxy functional silicones and fluoropolymers disclosed above.
Preferably the silicone, fluorosilicone and fluoropolymer functional layer pre-polymers have a number average molecular weight ranging from 2,000-60,000 Da and 0-30,000 mPas, i.e. suitable for solventless coating. Additionally, solvent can be used to dissolve higher molecular weight silicone and fluorosilicone pre-polymers. More preferably, the functional layer pre-polymers have number average molecular weights of 10,000-30,000 Da with viscosities of 200-20,000 mPas.
Crosslinkers and Cure Catalysts for Addition Cure Functional Layers
The pattern may be permanently retained in the functional layer by crosslinking using thermal and radiation cure (Infra red, ultraviolet or visible light and sources of scintillating radioactivity such as electron beams, gamma ray sources and the like) systems. For addition cure silicone pre-polymers, a nonlimiting list of silyl hydride crosslinkers include Dow Corning as homopolymers (Syl-Off™ 7048), copolymers (Syl-Off™ 7678) and mixtures (Syl-Off™ 7488). Crosslinker in the amounts corresponding to 1:1 to 10:1 silyl hydride:vinyl ratio was used with an appropriate amount of an inhibitor such as a 70:30 ratio of fumarate in benzyl alcohol to achieve good cure and adequate pot life in 100% solids coating dispersion with a thermal catalyst.
For addition cure silicone functional layer polymers, both thermal and ultraviolet ("UV") initiated platinum catalysts can can be used in the formation of release surfaces of the present invention. Nonlimiting examples of platinum thermal catalysts are Dow Corning (Midland, Mich.) Syloff 4000 and Gelest (Tullytown, Pa.) platinum-divinyltetramethyldisiloxane complex (SIP6830.0 and SIP6831.0). A nonlimiting example of a platinum UV catalyst is disclosed given by in U.S. Pat. No. 4,510,094 (Drahnak). Unlike the thermal catalyst, the UV catalyst does not require an additional inhibitor since the complex is effectively inhibited until exposure to UV.
Chemical Modifiers
Chemical additives or modifiers, as discussed in copending, coassigned, U.S. patent application Ser. No. 08/832,834 (Attorney Docket No. 53267USA7A can be added to the functional layer composition. These chemical additives may include higher molecular weight gums, particulate fillers, silicate resins, surface active agents, particulate fillers, etc.
Nonlimiting examples of silicone gums include vinyl functional gums ranging in molecular weights from 30,000 to 800,000 Da available from Gelest (DMS-41, DMS-46, DMS-52) and ethylenically unsaturated organopolysiloxane compositions prepared according to U.S. Pat. Nos. 5,468,815 and 5,520,978 (Boardman) and in European Patent Publication 0 559 575 A1 (the disclosures of which are incorporated by reference herein).
Preferably, the alkenyl-functional silicones have 2 to 10 carbon atoms with a molecular weight of approximately 440,000 Da. When silicone compositions were used as additives to low viscosity silicone pre-polymers in 100% solids formulations, their molecular weight was preferably less than 800,000 Da, more preferably less than 600,000 Da, and most preferably less than 500,000 Da. Their concentration was preferably less than 20% (w/w) in the silicone pre-polymer, more preferably less than 10% (w/w) and most preferably less than 5% w/w.
A nonlimiting list of fillers include hydrophobic filmed silica such as CAB-O-SIL™ TS-530, TS-610 and TS-720 (all from Cabot Corp. of Billerica, Mass.) and AER-O-SIL™ R812, R812S, R972, R202 (from Degussa Corp. of Rigdfield Park, N.J.). A non-limiting list of low surface energy fillers includes polymethylmethacrylate beads, polystyrene beads, silicone rubber particles, teflon particles, and acrylic particles. Other particulate fillers which can be used but which are higher surface energy include but are not limited to silica (not hydrophobically modified), titanium dioxide, zinc oxide, iron oxide, alumina, vanadium pentoxide, indium oxide, tin oxide, and antimony doped tin oxide. High surface energy particles that have been treated to lower the surface energy are also useful. The preferred inorganic particles include fumed, precipitated or finely divided silicas.
More preferred inorganic particles include colloidal silicas known under the tradenames of CAB-O-SIL™ (available from Cabot Corp.) and AEROSIL™ (available from Degussa). Hydrophobically treated colloidal silica, such as CAB-O-SIL™ TS-530, TS-610 and TS-720 (all from Cabot Corp. of Billerica, Mass.), are preferred. CAB-O-SIL™ TS-530 is a high purity hydrophobic fumed silica which has been treated with hexamethyldisilazane (HMDZ). CAB-O-SIL™TS-610 is a high purity hydrophobic fumed silica treated with dichlorodimethyl silane. CAB-O-SIL™ TS-720 is a high purity hydrophobic fumed silica treated with a dimethyl silicone fluid. The treatment replaces many of the surface hydroxyl groups on the fumed silica with a polydimethyl siloxane polymer. The treatment replaces many of the hydroxyl groups on the fumed silica with trimethylsilyl groups. As a result the silica is a low surface energy particle.
Most preferably the filler is a hydrophobically modified fumed silica treated in situ with HMDZ to chemically bind the silica to the pre-polymer, available from Nusil Corporation (Carpinteria, Calif.). The composition of the hydrophobic filler is preferably 0.1 to 20%, more preferably 0.5 to 10% most preferably 1 to 5% w/w.
A non-limiting list of silicate resins include Dow Corning 7615, Gelest vinyl Q resin VQM-135 and VQM-146 which are provided as dispersions of silicate in silicone. Preferably, the silicate resin is present at 5 to 100% w/w in the silicone pre-polymer, more preferably 0 to 75%, most preferably 0 to 50% (w/w).
A nonlimiting list of surface active agents include low molecular weight acrylate based surfactants such as Modaflow (Monsanto, St. Louis, Mo.) and BYK-358 (BYK-Chemie), silicone-functional surfactants such as Silwets (OSI), and fluorochemical surfactants such as Fluorads (3M, St. Paul, Minn.) and Zonyl (Dupont, Wilimington, Del.) leveling agents.
The mean thickness of the functional layer is preferably about 0.005 to 100 microns, more preferably about 0.01 to 25 microns and most preferably about 0.1 to 5 microns.
The substrate can be a continuous web, discrete sheets or rigid piece parts, or an array of pieces or parts transported through the coating. Nonlimiting examples of substrates include opaque, translucent, and clear substrates; low surface energy and high surface energy substrates, textured, patterned, rough, and smooth substrates; and combinations thereof. Preferred continuous webs include transparent, translucent or opaque materials of low to high surface energy. More preferably the substrate may include polyethylene terephthalate, polycarbonate, polystyrene, and an inverted dual layer photoreceptor as described in Example 6 of PCT Patent Publication WO 96/34318 and U.S. application Ser. No. 08/431,022. Most preferably, the substrate is clear polyester.
Dispensing of the Composite of Carrier Fluid Layer and Functional Fluid Layer
Nonlimiting examples of dispensing of the composite of carrier fluid and functional fluid include dip coating, bath coating, carrier fluid coating, multilayer curtain coating, multilayer extrusion die coating, roll coating, spray coating and drip coating. Of these coating methods, carrier fluid coating and bath coating are preferred.
Carrier Fluid Coating Process Parameters
International Patent Publication WO 96/23595 (Melancon et al.), the disclosure of which is incorporated by reference herein, discloses the general parameters for use of a carrier layer of fluid (such as water) to transport a functional layer (such as silicone or other polymeric material) to a web. A preferred method is curtain coating of the composite layer.
As used in the present invention, carrier layers are preferably water and non-aqueous but water miscible liquids, more preferably water, salt solutions, and aqueous surfactant solutions, and most preferably tap water. The concentration of water in the carrier layer is preferably about 0 to 100%, more preferably about 50 to 100%, most preferably greater than 99% (w/w).
While Melancon et al. describe general processing parameters, the following parameters are important to an understanding of the scope of the present invention.
The web speed of the continuous process is preferably about 0 to 5000 m/min, more preferably about 2 to 1000 m/min, and most preferably about 10 to 300 m/min.
The curtain height is preferably about 0 to 30 cm, more preferably about 1 to 15 cm, most preferably about 2 to 5 cm. The angle of the curtain relative to the substrate is preferably about 0 to 90 degrees, more preferably about 20 to 60 degree, more preferably about 40 to 50 degrees.
Surface coverage of the pattern is preferably about 0.1 to 99% of the surface area, more preferably about 5 to 99% of the surface area, and most preferably 20 to 99% of the surface area.
Patterning can form in a a variety of geometric patterns based on control of other parameters discussed herein. For example, control of fluid flow can alter patterns in a regular fashion, leading to a Euclidean geometric pattern.
Optical clarity is preferably clear to opaque, depending on the use of the coating.
The variation of thicknesses across surface area at the microscopic level is preferably about 0 to 10 microns, more preferably about 0 to 5 microns, most preferably about 0 to 2 microns.
Drying patterns (for example, Benard cells) may also be used to generate surface textures on release surfaces. However, the mechanism of this invention is by a different means. The mechanism of drying pattern formation either by density gradients caused by temperature gradients in a coating or by surface tension gradients is described in E. Cohen and E. Gutoff, "Modern Coating and Drying Technology," (VCH Press: NY, 1992), pp. 132-94 and Velarde and Normand, "Convection," Scientific American, 243, 92 (1980). For wet coating thicknesses less than 1 mm, convection cells are almost always driven by surface tension. The formation of surface tension driven convection patterns (Benard cells) is predicted by the magnitude of the Marangoni Number: ##EQU1## where (dσ/dT) is variation of coating fluid surface tension with temperature, (dT/dy) is the temperature variation across the thickness of the wet coating, h is the wet coating film thickness, η is the shear viscosity of the coating fluid, k is the thermal conductivity of the coating fluid, ρ is the density of the coating fluid and Cp is the liquid heat capacity at constant pressure of the coating fluid.
For thick coatings (i.e. wet film thickness>1 mm), surface tension driven instabilities will occur for Ma>80, however, Cohen and Gutoff note that critical Marangoni Number will be lower for thinner coatings. Marangoni instabilities will thus be enhanced by increasing the surface tension gradient with temperature (dσ/dT), the temperature gradient with wet coating thickness (dT/dy), and the wet film thickness (h). Similarly, Marangoni instabilities will be decreased by increasing fluid viscosity (η), increasing fluid thermal conductivity (k), increasing fluid density (ρ) or decreasing fluid heat capacity (Cp).
This invention extends beyond prespresent art by relying on the presence of three components that contribute to the creation of patterning of the coating on the substrate: the functional layer of the coating, the carrier layer of the coating, and the substrate on which the layers contact. The ability of the two layers of the coating to generate patterns prior to the evaporation or other removal of the carrier layer is a feature of the present invention. Only when both the functional layer and the carrier layer are in contact with the substrate does the possibility of interfacial interaction among the two layers and the substrate occur. This interfacial interaction contributes to the formation of the patterning of the functional layer on the substrate.
Bath Coating Process
Functional layers include the same layers as the carrier fluid coating process, described above and Melancon WO 96/23595.
The bath can use the same liquids as a carrier layer in the carrier fluid coating process, as described above and in Melancon WO 96/23595.
The following parameters are important to an understanding of the scope of the present invention.
The web speed of continuous process is preferably about 0 to 5000 m/min, more preferably about 2 to 200 m/min, and most preferably about 10 to 30 m/min.
The variation of thicknesses across surface area at microscopic level is preferably about 0 to 10 microns, more preferably about 0 to 5 microns, most preferably about 0 to 2 microns.
Patterns produced according to the method of the present invention include those having inhomogeneity in thickness, spacial resolution and maerial composition, and combinations thereof across and down a substrate during the transferring step to the substrate. Variation in the pattern can be selected from the group consisting of random, symmetrical, periodic, gradual, irregular, circular, angular, non-angular, and combinations thereof. Further the patten can result in characteristics such as a matte finish, optical transmittance, roughness, porosity, image quality, controlled release, partial coating, and combinations thereof
Regardless of the type of coating process employed, the invention optionally comprises a further step of removing the carrier fluid from the substrate. Nonlimiting examples of method to remove carrier fluid include mechanical doctoring, gravity, centripetal removal, blowing, suction, solidification of carrier and doctoring, absorption into an absorptive material, gelation of carrier and doctoring, gelation of coating and doctoring, adsorption of carrier fluid, and evaporation.
Regardless of the type of coating process employed, the invention optionally comprises a further step of post-processing a functional fluid layer on the substrate. Nonlimiting examples of post-processing include drying to retain the pattern already formed in step (c), crosslinking, and separating the patterned coating from the substrate, and combinations thereof.
Usefulness of the Invention
The processes of the present invention can be used to formulate premium release surfaces by modulating the release characteristics. It can also be used to alter the optical clarity of a coating, i.e. from a glossy to translucent appearance. In another application, this coating process can be used to generate a porous, polymeric membrane.
Modulation of coating patterns is useful for controlling release characteristics, optical clarity or porosity of coatings. Generation of patterned release surfaces for optical photoreceptors for liquid electrography is demonstrated in copending, coassigned, U.S. patent application Ser. No. 08/832,543, abandoned (Baker et al.) (Attorney Docket No. 53268USA7A), the disclosure of which is incorporated by reference herein. Translucent or matte release surfaces (such as the translucent coatings generated here) can also be useful to reduce the appearance of defects in release coatings used for tapes. Patterned release surfaces may be used to control peel forces, allowing the coating method (rather than the chemistry) to be used to "fine tune" the release properties for specific applications. Patterned release coatings may be useful for medical tapes, where the pattern may modulate the characteristics of the peel from skin or other tissue. Patterned coatings may also be used to control the relative barrier and permeability characteristics of coatings. Moisture vapor permeability (MVT) may be affected, and thus this process may find application in medical tapes that require high MVT. Porous membranes and patterned films may be generated by this technique, and may find utility in controlling flow of liquids and gases.
These patterning processes can be used with 100% solids formulations, which are more environmentally benign. These patterns can be applied at coating thicknesses ranging from about 0.005 to 1000 microns. The methods of pattern generation have the advantage of bearing minimal tooling cost for changing and controlling patterns.
These methods of generating patterned surface release layers are also useful as elements of temporary receptors, as would be used for electrography, particularly electrophotographic and electrostatic printing, as discussed in copending, coassigned, U.S. patent application Ser. Nos. 08/832,834; 08/832,543, abandoned and 08/828,823.
Further embodiments and uses are described the following examples.
Raw Materials
The raw materials used consisted of curable and non-curable silicones and fluorosilicones. Addition curable, ethylenically unsaturated silicones were prepared by methods known in the art (including U.S. Pat. No. 4,609,574) and commercially obtained from Dow Corning (Syl-Off 7240; Midland, Mich.), Gelest (VDT-731; Tullytown, Pa.), United Chemical Technologies, Inc. (PS444 and PS445; Bristol, Pa.), and Nusil Technologies (PLY7500; Carpinteria, Calif.).
Release materials included base silicone or fluorosilicone addition cured pre-polymers in combination with homopolymer and/or copolymer hydride cross linkers. These pre-polymers represented a range of potential crosslinking density, afforded by the presence or absence of pendant crosslinkable groups in addition to crosslinkable endcapping groups as well as a range of (low) molecular weights, thus enabling low viscosity solventless coating formulations. The mole percent of crosslinkable groups varied between 1-10% in the pre-polymer. Both vinyl and alkenyl crosslinking groups were used. The molecular weights of the pre-polymers ranged from approximately 10,000-30,000 Da, with the lower molecular weights corresponding to useful viscosity ranges for solventless coating methods and yielding a higher effective cross link density.
Other functional silicones and fluorosilicones were also used, including epoxy functional silicone GE UV9300 (General Electric Company, Waterford, N.Y.) and mixed epoxy functional silicones (MES) prepared according to Example 1 in Kessel and Nelson in U.S. Pat. No. 5,332,797. In addition, non-crosslinkable polydimethylsiloxane viscosity standards (Brookfield Engineering Laboratories, Stoughton, Mass.) were also used. Silicone pre-polymers were also used in the absence of crosslinker and cure systems. Silicones and fluorosilicones varied in molecular weight from 10,000-30,000 Da, corresponding to useful viscosity ranges for solventless coating methods (i.e. 1-30,000 mPas).
Table 1 summarizes some of the materials used, together with their equivalent weights.
Both thermal and ultra-violet ("UV") initiated platinum catalysts were used. Examples of platinum thermal catalysts are Dow Corning (Midland, Mich.) Syl-Off 4000 and Gelest (Tullytown, Pa.) platinum-divinyltetramethyldisiloxane complex (SIP 6830.0 and 6831.0) An appropriate amount of a 70:30 mixture by weight of diethyl fumarate and benzyl alcohol (FBA) can be added as an inhibitor or bath life extender as taught in U.S. Pat. Nos. 4,774,111 and 5,036,117. A platinum UV catalyst was also used and was prepared as described in L. D. Boardman, Organometallics, 1992, 11, 4194-4201 and in U.S. Pat. Nos. 4,510,094 and 4,600,484 (Drahnak), the disclosures of which are incorporated by reference herein.
Silyl hydride cross linkers were obtained from Dow Corning as homopolymers (Syl-Off7048), copolymers (Syl-Off7678) and a 1:1 mixture (Syl-Off7488).
Crosslinker in the amount corresponding to 1.3:1 to 5:1 silyl hydride:vinyl ratio was used in combination with 2.40% w/w FBA in the base pre-polymer to achieve good cure and adequate pot life in 100% solids formulations. In other experiments, the formulation contained only the silicone pre-polymer, and did not include crosslinker or cure system.
Additives were used in these formulations, including hydrophobic silica (CAB-O-SIL™ TS-530 and TS-720 (all from Cabot Corp. of Billerica, Mass.) and hexamethyldisilazane in-situ treated silica in silicone (from Nusil of Carpinteria, Calif.). A coefficient of friction modifying, high molecular weight silicone gum was prepared according to the methods described in Boardman etal, U.S. Pat. Nos. 5,520,978 and 5,468,815 and was also used in some formulations. Surface active agents (SAA) included Fluorad FC431 (3M of St. Paul, Minn.), Silwet L77 (OSI Specialties, Inc. of Danbury, Conn.), Modaflow III and Modaflow 2100 (Monsanto Corp. of St. Louis, Mo.) and BYK-358 (BYK-Gardner of Columbia, Md.). Heptane was added to some samples to investigate the effect of viscosity and surface tension.
For the solventless coating formulations, Stock A contained the base silicone, gum, platinum catalyst, and a fumarate inhibitor. A fully reactive system was prepared just prior to coating by the addition of Stock B (containing the cross linker). Examples of these formulations are described in Table 2 for ethylenically unsaturated addition cure polymers. Similar formulations were prepared for vinyl functional base polymers.
TABLE 1______________________________________Summary of Material Set Description (crosslinking mole % Viscosity MW1Component functionality) vinyl (mPas) (g/mol)______________________________________PRE-POLYMERSI hexenyl pendant and 2.67 450 9600 endblockedII hexenyl endblocked only 1 450 12400______________________________________ 1 Approximate molecular weight calculated from degree of polymerization (dp).
TABLE 2______________________________________Example Preparation of Stocks A and B for Solventless ReleaseFormulations Final ConcentrationComponents (relative to base polymer) Amount (g)______________________________________Stock ABase silicone I -- 833.25Syl-Off Syloff 4000 0.52% w/w 19.83Pt thermal catalystFBA Inhibitor 2.4% w/w 19.80Stock BCrosslinker Syl-Off 7048 5:1 Silyl hydride:vinyl 135.12______________________________________
Coating Methods
Coating substrates included 12"(38 cm) wide clear polyester film, aluminized PET, and an inverted dual layer photoconductor with barrier layer (the formulation of which has been described in U.S. application Ser. No. 08/431,022 Example 6, the disclosure of which is incorporated herein by reference).
Carrier Fluid Coating Process
A two layer slide die was used, as described in International Patent Publication WO 96/23595. Silicone flowed from the top slot, which had a 0.254 mm gap. Water flowed through the bottom slot, which had a 0.508 mm gap. Both slots were 248 mm wide. Municipal tap water was used as the carrier layer. The water flow rate out of the bottom die slot varied between 2.2 to 2.8 L/min (corresponding to pump rates of 21 to 22.6 rpm). The typical water temperature was 10 to 13 degrees C., except during experiments specifically designed to test the effect of higher water temperature. In these cases the water temperature was varied in a range from 10 to 66 degrees C. The thickness of the coating was controlled by varying the syringe pump rate (which metered the release formulation into the die) or by changing the web speed. Coating thickness was varied between 0.1-2 microns. Typical web speeds were 3-30 m/min. Typical syringe pump rates ranged from 1 to 5 milliliters per minute.
Langmuir Blodgett Bath Coating Process
Langmuir Blodgett Bath coating was also used. A functional layer such as silicone was applied to the surface of a water bath and drawn up onto a moving web as the web kissed the bath surface via a coating roll. The effect of temperature on this process was studied by examining the coating characteristics resulting when the bath was filled with cold water (10 degrees C.) or hot water (50 degrees C.).
Conventional Gravure Coating Process
Direct, forward offset, and reverse offset gravure methods were also used to coat samples. These methods were used to achieve a coating thickness in the target range of 0.3-2 microns for comparison to the water carrier-based processes of carrier fluid coating process and bath coating. Experiments were done on two different coating lines, one with a 3 m infrared oven and the other with a 3 m air floatation dryer. Gravure rolls with pyramidal cells having volume factors of 3-7.7 cubic billion microns were used. Web speeds were 3, 15 and 30 meters per minute (m/min). Gravure roll speeds were varied from 1 to 13.6 m/min. Gravure roll speeds were adjusted to thicken or thin a coating depending on feedback from an on-line UV gauge.
Coating thickness
The coating thickness in the gravure experiments was measured using an on-line UV gauge in a manner as disclosed in U.S. Pat. Nos. 3,956,630; 4,250,382; 4,978,731; and 4,922,113, the disclosures of which are incorporated by reference. A UV dye was mixed into the coating in a 1% (w/w) concentration. The dye in the coating was excited by UV light and the signal it emitted was proportional to coating thickness. An on-line calibration curve was generated by running the web line at a known speed and using a syringe pump to meter a known coating volume onto the web under a spreading bar. The relationship of fluorescence intensity to coating was linear in the range of interest (i.e. from 0.1-1 micron).
Optical Microscopy
A Zeiss Axioskope microscope was used to examine coatings using a magnification of 50� with a differential interference contrast lens with both reflected and transmitted light. Images were recorded with a Polaroid camera on black and white film.
Example 1 illustrates the nature of the patterns generated by a fluid carrier coating process. The fluid carrier coating process was used to coat a functional layer of ethylenically unsaturated silicone I onto polyethylene terephthlate (i.e., polyester) substrate using water as the fluid carrier. As shown in FIG. 1 and Example 1.1 (Table 3), prominent and consistent patterns were seen on the substrate that vary in dimension with the thickness of the functional layer. These patterns were observed after the coater, but before the oven where the coatings were heat cured. These coatings could be crosslinked to preserve the pattern. At a coating thickness of approximately 1.1 microns, the coating was shown to exhibit a prominent orange peel texture, as shown in FIG. 1 A. This texture became finer as the coating thickness was reduced, showing smaller, more circular holes at 0.52 and 0.26 microns (FIGS. 1B and 1C, respectively). At coating weights corresponding to 0.13 microns (FIG. 1D), the pattern was almost indiscernible by eye; the marked characteristic of the coating was its translucent or matte finish (as opposed to glossiness).
The functional layer I (as described in Table 1) was coated onto polyester substrate using a Langmuir bath coater and direct gravure. Again, the formulation I consisted of a 100% solids formulation. Web speed and gravure roll ratios and cell patterns were chosen such that the thickness of the resulting functional layer was comparable in the three coating methods, i.e., at 0.5 microns. The coating patterns are described in Table 3. When a Langmuir bath coater was used with water as the carrier fluid, similar small round "pinhole" patterns were found in the functional layer as when the fluid carrier coating process was used (FIG. 1B and Examples 1.1 and 1.2). In contrast, as shown in Example 1.3, when gravure was used with the same 100% solids formulation and polyester substrate, but with no water (or fluid carrier layer) present, no pinhole patterns were seen. Rather, the gravure pattern was evident.
TABLE 3__________________________________________________________________________Comparison of Coating Patterns Generated by CarrierFluid Coater, Bath Coater and Gravure Functional Web Coating Viscosity pump rate speed Thickness TempEx Method (mPas) (mL/min) (m/min) (microns) (C.) Coating Quality__________________________________________________________________________1.1 Carrier 450 1.0 7.6 0.52 10 isolated pinholes Fluid cover the web Method (orange peel); water forms pearls down center of web1.2 Bath 450 1.0 7.6 0.52 10 round "pinhole" Coater pattern similar to Carrier Fluid Coating method1.3 Direct 450 NA 15.2 0.6 ? 21 some downweb and Gravure rubber roll marks; very good coating quality; gravure pattern seen__________________________________________________________________________
The absence of similar patterns with the gravure process supports the concept that the orange peel or circular patterns are not due only to an interaction between the coating material and the substrate The presence of the fluid carrier is critical to pattern generation. While not wishing to be bound by any particular theory, it is believed that the interaction of the substrate, fluid carrier, and functional layer is essential for pattern generation.
Example 2 in Table 4 illustrates that fluid carrier coating methods can be used to generate and control patterns for silicone functional layers possessing different molecular weights, viscosities and crosslinking functionality. As shown in Table 4, within each silicone series, thinner coatings show finer patterns. Surface patterns of silicones possessing local high energy functional groups, such as the epoxy silicones (Examples 2.1-2.8), show finer patterns or more translucent coating (less obvious orange peel) at similar coating thicknesses compared to alkenyl functional silicones (Examples 2.9-2.20).
As shown in Table 4, higher viscosity silicones (corresponding to higher molecular weights) correspond to finer patterns at similar coating weights. This is seen readily in Example 2.20 (10,000 mPas) compared to Example 2.10 (450 mPas). As shown in Example 2.21, solvent can be added to the formulation to change patterning behavior.
TABLE 4__________________________________________________________________________Effect of Silicone Functionality on Carrier Fluid Coating Process CoatingPatterns atVarying Formulation Viscosities and Coating Thicknesses Functional Water Web Functional Viscosity pump rate Flow Rate speed Thickness TempEx Layer (mPas) (mL/min) (L/min) (m/min) (microns) (C) Coating Quality__________________________________________________________________________2.1 GE UV 230 1.0 2.6 3.8 1.1 10 shiny, tiny dots on the web 93002.2 GE UV 230 1.0 2.6 7.6 0.52 10 more dots on the web 93002.3 GE UV 230 1.0 2.6 15.3 0.26 10 many more dots than 2.2; 9300 translucent; irregular wetting patterns are apparent2.4 GE UV 230 1.0 2.6 30.5 0.13 10 coating is very translucent 93002.5 MES 300 1.0 2.6 3.8 1.1 10 shiny, tiny dots on the web2.6 MES 300 1.0 2.6 7.6 0.52 10 more dots on the web2.7 MES 300 1.0 2.6 15.3 0.26 10 many more dots; translucent2.8 MES 300 1.0 2.6 30.5 0.13 10 coating is very translucent in appearance__________________________________________________________________________
__________________________________________________________________________ Functional Water Web Functional Viscosity pump rate Flow Rate speed Thickness TempEx Layer (mPas) (mL/min) (L/min) (m/min) (microns) (C) Coating Quality__________________________________________________________________________2.9 I 450 1.0 2.6 3.8 1.1 10 prominent fishnet or orange peel pattern with large circular holes and dewetting patterns2.10 I 450 1.0 2.6 7.6 0.52 10 orange peel effect2.11 I 450 1.0 2.6 15.3 0.26 10 finer scale orange peel than 2.10 - but still prominent2.12 I 450 1.0 2.6 30.5 0.13 10 fine dewetting pattern or holes, translucent, looks like epoxy silicones2.13 Nusil PLY 1000 1.0 2.6 3.8 1.13 10 prominent orange peel 75002.14 Nusil PLY 1000 1.0 2.6 7.6 0.52 10 finer but obvious orange peel 75002.15 Nusil PLY 1000 1.0 2.6 15.3 0.26 10 very fine orange peel 75002.16 Hulls 5000 1.0 2.6 3.8 1.13 10 tiny holes visible to the eye PS444__________________________________________________________________________
__________________________________________________________________________ Functional Water Web Functional Viscosity pump rate Flow Rate speed Thickness TempEx Layer (mPas) (mL/min) (L/min) (m/min) (microns) (C) Coating Quality__________________________________________________________________________2.17 Huls PS444 5000 1.0 2.6 7.6 0.52 10 tiny holes in a dense pattern and no water dewetting streaks2.18 Huls PS444 5000 1.0 2.6 15.3 0.26 10 very grainy texture, tiny densely packed holes; slight water droplet dewetting patterns2.19 Huls PS445 10,000 1.0 2.6 3.8 1.1 10 tiny holes and a speckled web (but fewer than 2.18)2.20 Huls PS445 10,000 1.0 2.6 7.6 0.52 10 very tiny, readily discernable dots; grainy2.21 I and <<450 2.0 2.6 7.6 0.52 10 orange peel, many water heptane patterns on the web, (1:1) dewetted areas__________________________________________________________________________
Example 3 in Table 5 and FIG. 2 further illustrate the effect of functional layer viscosity on pattern generation with a fluid carrier coating method. The effect of viscosity was examined using polydimethylsiloxane viscosity standards, purchased from Brookfield. As shown in FIG. 2a, prominent orange peel was seen with a 500 mPas silicone, similar to that shown in FIG. 1b for the similar viscosity alkenyl functional silicone (I). At higher viscosities, such as 30,000 mPas in FIG. 2b, the coating was glossy with only very tiny circular patterns, generating a translucent or matte finish. However, downweb ribbing patterns were apparent in the coating. Additional results are shown in Examples 3.1 to 3.12 for a series of viscosity standards (480-30,000 mPas) coated at thicknesses ranging from 0.26 to 1.1 microns. Example 3 demonstrates that for a homologous series of functional layer polymers, patterns can be controlled through appropriate choice of viscosity and coating weight. Patterns can be modulated to achieve glossy, translucent (or matte finish), or porous coatings. In constrast to gravure coating, no retooling costs are required for pattern control.
TABLE 5__________________________________________________________________________Effect of Coating Thickness and Viscosity on Modulating theRelease Coating Pattern Characteristics Generated by Carrier FluidCoating Functional Water WebViscosity pump rate Flow Rate speed Thickness TempExample(mPas) (mL/min) (L/min) (m/min) (microns) (C) Coating Quality__________________________________________________________________________3.1 480 1.0 2.6 3.8 1.1 10 large circular craters and dewetting patterns; translucent3.2 480 1.0 2.6 7.6 0.52 10 finer circular craters and dewetting patterns that Ex. 1.1; translucent3.3 480 1.0 2.6 15.3 0.26 10 finer circular craters and dewetting patterns than 3.2 - still very visible3.4 1000 1.0 2.6 3.8 1.1 10 large, obvious dewetted areas3.5 1000 1.0 2.6 7.6 0.52 10 shiny coating with tiny holes; these did not dewet to form craters3.6 1000 1.0 2.6 15.3 0.26 10 many tiny holes; coating is__________________________________________________________________________ translucent
__________________________________________________________________________ Functional Water WebViscosity pump rate Flow Rate speed Thickness TempExample(mPas) (mL/min) (L/min) (m/min) (microns) (C) Coating Quality__________________________________________________________________________3.7 11,800 1.0 2.6 7.6 0.52 10 shiny coating with very tiny holes that are visible under a microscope3.8 11,800 1.0 2.6 15.3 0.26 10 more tiny holes in coating3.9 11,800 1.0 2.6 24.4 0.16 10 many tiny holes in coating3.10 30,000 1.0 2.6 3.8 1.1 10 tiny holes are visible only as dots to the eye; difficult to get good crossweb distribution with this viscosity3.11 30,000 1.0 2.6 7.6 0.52 10 shiny coating; very tiny holes, downweb interference patterns (stripes)3.12 30,000 1.0 2.6 15.3 0.26 10 shiny coating, very tiny holes in somewhat greater number than__________________________________________________________________________ 4.11
Example 4 illustrates the effect of altering the surface tension gradient between the water and the silicone by adding surface active agents (SAA's) to the silicone phase. SAA's can also be used in the fluid carrier.
TABLE 6__________________________________________________________________________Effect of Surface Tension Modifiers and Leveling Agents onPatterned Release Surfaces Generated by Fluid Carrier Coating Process Functional Water Web Viscosity pump rate Flow Rate speed Thickness TempEx SAA (mPas) (mL/min) (L/min) (m/min) (microns) (C) Coating Quality__________________________________________________________________________4.1 II + 1% Silwet 450 1.0 2.6 7.6 0.52 10 shows exaggerated patterns L774.2 II + 0.5% 450 1.0 2.6 7.6 0.52 10 shows exaggerated patterns Fluorad FC-4314.3 I + 0.5% 450 1.0 2.6 7.6 0.52 10 reduced patterns; showed Modaflow resin brushstroke patterns__________________________________________________________________________
__________________________________________________________________________ Functional Water Web Viscosity pump rate Flow Rate speed Thickness TempEx SAA (mPas) (mL/min) (L/min) (m/min) (microns) (C) Coating Quality__________________________________________________________________________4.4 I + 0.25% 450 1.0 2.6 7.6 0.52 10 rough micromixture; no round Modaflow 2100 holes but dewetting marks and tranlucent coating4.5 I + 1.0% 450 1.0 2.6 7.6 0.52 10 translucent; irregular wetting Modaflow 2100 patterns; wetting streaks4.6 Nusil 1000 1.0 2.6 7.6 0.52 10 obvious finer orange peel PLY7500 + HMDZ (similar to silicone without silica (3% TS530) silica); good curtain stability - better than formulations with unbound silica4.7 Nusil 1000 1.0 2.6 7.6 0.52 10 difficult to maintain a stable PLY7500 + curtain; seashore coating 3% TS530 pattern and dark silica agglomerates__________________________________________________________________________
As shown in Examples 4.1 and 4.2, addition of silicone or fluorine containing SAA's can induce severe patterning of the coating compared to Examples 2.10 and 3.10. Use of a leveling agent, such as Modaflow, can attenuate the patterns to show a brushstroke texture, matte or translucent coating (Examples 4.3 and 4.4). Increasing the concentration of Modaflow 2100 can lead to wetting streaks from the water carrier fluid dewetting and irregular coating patterns (Example 4.5). Including hydrophobic bound silica (for example hexamethyldisilazane in situ treated silica, Example 4.6) leads to a similar, fine orange peel pattern like Example 2.14 (which contains the same silicone without silica). Use of an HMDZ-in situ treated silica is preferred over unbound hydrophobic silica for the water carrier process, because the unbound silica gave a very unstable water curtain (Example 4.7). Water drainage patterns associated with the incorporation of SAA's (as illustrated in Examples 4.3 and 4.5) may be reduced or eliminated by using an air bar for water removal in the carrier fluid coating process set up (instead of relying solely on drainage).
In addition to including a SAA in the formulation (or in the water curtain), the temperature of either the water or the silicone (or both) can be altered to change the surface tension. This is illustrated in Example 5 in Table 7 in which the water temperature was varied between 10 to 30 degrees C. in a carrier fluid coating process. The functional layer formulation consisted of alkenyl functional silicone I. The coating substrate was clear polyester.
TABLE 7__________________________________________________________________________Modification of the Surface Tension of Water through Adjustingthe Temperature of Fluid Carrier Functional Water Web Viscosity pump rate Flow speed Thickness TempEx (mPas) (mL/min) (L/min) (m/min) (microns) (C) Coating Quality__________________________________________________________________________5.1 450 1.0 2.2 7.6 0.52 10 orange peel5.2 450 1.0 2.2 7.6 0.52 38 orange peel5.3 450 1.0 2.2 15.3 0.26 38 finer orange peel5.4 450 1.0 2.2 7.6 0.52 49 a little finer orange peel than control5.5 450 1.0 2.2 15.3 0.26 49 air entrained5.6 450 range 2.2 range range 66 at all speeds and pump rates, the curtain was unstable; fine orange is the small amounts that could be coated; much turbulance and downweb chatter__________________________________________________________________________
Conditions were chosen to give an orange peel pattern at 10 degrees C. for the control (Example 5.1). As the temperature was increased to 38 and 49 degrees C., a much finer pattern was achieved (Examples 5.3 and 5.4). At higher web speeds at 49 degrees C., air was entrained so a coating was not deposited (Example 5.5). At 66 degrees C., the curtain was unstable (Example 5.6), resulting in much turbulence and downweb chatter (or seashore patterns). However, we note that in coated portions of the web at 66 degrees C., the pattern size was very fine. A slot size larger than 0.51 mils and a higher flow rate may improve the stability of the curtain and make coating at this temperature possible. We also note that with the present die design for carrier fluid coating process, heating the water also resulted in heating the silicone. The die could be redesigned to preferentially use temperature to alter the surface tension and viscosity of one phase relative to the second phase.
Coatings were also made on the bath coater at elevated temperatures. At 59 degrees C. and 15 m/min, silicone formulation I was observed to "neck" into the water, rather than spreading evenly onto the polyester substrate. Addition of a SAA such as 0.5% BYK-358 caused the silicone to spread chaotically on the bath surface.
Examples 3, 4 and 5 illustrate a general approach for controlling patterns in coating processes using a fluid carrier, namely, modifying the surface tension of the water and/or oil phase in combination with process and formulation parameters (such as coating thickness, viscosity, etc.). Surface tension modifiers in these examples include (but are not limited to) SAA's (surfactants, wetting agents, leveling agents, particles, etc.) and temperature.
The invention is not limited to the above embodiments. The claims follow.
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|International Classification
|Cooperative Classification
|European Classification
|Sep 22, 1997
Owner name: MINNESOTA MINING AND MANUFACTURING COMPANY, MINNES
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BUTLER, TERRI L.;BRETSCHER, KATHRYN R.;BERENS, MARK C.;AND OTHERS;REEL/FRAME:008719/0418;SIGNING DATES FROM 19970909 TO 19970912
|Jan 24, 2003
|Fee payment
Year of fee payment: 4
|Jan 29, 2007
|Fee payment
Year of fee payment: 8
|Feb 28, 2011
|Maintenance fee reminder mailed
|Jul 27, 2011
|Lapse for failure to pay maintenance fees
|Sep 13, 2011
|Expired due to failure to pay maintenance fee
Effective date: 20110727


text:
I was walking a long and found this and I saw this little bumble bee just laying there on the railing. At first I thought that it was dead and started to take shots of the bee, thinking "awww…. what a cute little bee, poor guy". But then he start moving after an ant had bitten his foot: so I then I thought "while I guess he was just tired or a very, very,………..very, lazy bee".
Plz, don't use without permission.

subset: commoncrawl


text:
Officer-Involved Shootings
FULL LIST OF Officer-Involved Shootings - page 28 Videos
P1 Weekly Update for 12/21/12 - Dave Smith reviews this week's news, recalling the Sandy Hook shooting and the history of mass killings, cop casualties, and another 'not today' incident.
P1 Weekly Update for 12/14/12 - PoliceOne's Dave Smith reviews the news for the week of December 14, analyzing an Oregon mall shooting, an abnormal number of K-9 deaths, and the rescue of a newborn by police officers.
Chief's message on officer injuries - After a spur of officer-involved violent incidents, the Portland police chief released a video to his officers to rally department members and show his support.
Legacy of the Lakewood Four - This P1 exclusive video tells the story of the Lakewood ambush from the perspective of Washington state law enforcement.
Survival Story: December 1988 Shooting - Officer Jill Ehlers recalls an incident in which she was involved in a deadly shooting involving a suspect on drugs who was wanted for the assault of a police officer.
Dash cam: Man fatally shot after attacking cops - Footage was just released of a July incident in which two officers were attacked by a suspect and both the male and female officer fired back.
Cop pulls woman by hair away from burning home - A San Diego police sergeant was videotaped apparently pulling a woman's hair as he and her husband tried to keep her away from her burning home.
Skater tells off cop - Student is irate at police officer, claiming the officer almost ran him over, and demands apology.
Denver police investigate fatal shooting - Denver police are investigating a shooting that killed one person.
Robbery suspect fires at cops, is killed - Read the full story: http://www.policeone.com/Patrol-Video/articles/5932786-Video-Robber-opens-fire-on-Fla-officers-is-killed/
Reality Training: Kansas City Park Shooting - Watch how officers exhibit model contact and cover communication after a suspect shot directly at them in a Kansas City Park.
Reality Training: Expect the Unexpected - Betsy Brantner Smith reviews how officers respond to a spontaneous gunfight and safely stop the threat while protecting a woman and child in the process.
Reality Training: Trolley Square Shooting - In this segment, Barb Harris and Betsy Brantner-Smith discuss the Trolley Square Shooting and the importance of talking with and preparing your family for the role you play as a law enforcement officer both on and off duty.
Instinctive Point Shooting - 75 percent of gunfights occur at a distance of less than 20 feet. In this video, Ray DeCunto discusses 5 distinctive point shooting fundamentals: Grip, draw, trigger control, stance, and when to shoot.
Alexis Artwohl: Job Stress - Memory & Decision Making - In this segment, Doug Wyllie consults with veteran psychologist Alexis Artwohl about her research working with officers who have experienced post-shooting distress.
PoliceOne top 5
1 Video: Okla. cop fatally shoots suspect after struggle over service weapon
2 Union mad police victims have voice at DNC, not cops' widows
3 Taco Bell employee fired after denying service to deputies
4 Kan. officer shot to death while looking for drive-by suspect


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The 2011 Mercedes-Benz C63 AMG DTM Safety Car
Watch the video: The 2011 Mercedes-Benz C63 AMG DTM Safety Car What is it about racing that inspires drivers to go all out on the track? Is it the hunger for victory? Or perhaps the fame and glory? Whatever it is, there's got to be someone on the sidelines ready to pounce in just in case a driver goes too wild or something goes wrong mechanically. For this year's DTM racing series, that role is bestowed upon the 2011 Mercedes-Benz C63 AMG Safety Car. If you know your motorsports, it won't be any surprise to you that despite all the hardwork and inspiration put into the base sedan by AMG, it'll… Continue Reading »


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ADA Info
June 6- August 6
Did you get a cool new laptop or smartphone over the winter break and wonder how to better use it? If so, please join us in the upstairs Training Lab on Friday, January 15 at 10:30 AM for TGIF Programs' Technology Question and Answer Series. This will be a great time to ask Freeman Library staff about computers, smartphones, devices, and eContent.
All TGIF Programs events are free and no registration is required. Refreshments are provided by the Friends of Freeman Library. Please contact the Clear Lake City - County Freeman Branch Library at 16616 Diana Lane, Houston, TX 77062 or at 281-488-1906 for further information.
Babies from infants through 18 months old have somewhere to be this Friday, January 15 at 10:00 am! They and their parent or caregiver are invited to hang out in the Children's Activity Space for Baby Playtime. This program is held several times a year as a special chance for babies and their adults to spend time together with board books, fun toys, and bubbles. We also will have an art project for the babies and we will debut a new item for the babies to explore! No tickets are needed for this program. A special thanks to the Friends of Freeman Library for their continued support for this program through the fun items we're able to purchase.
Registration is now full. Waiting List is Open until Tuesday, January 26, 2016.
If you are at least 50 years old, then we hope you will join us on a day trip to the Museum of Fine Arts – Houston and the Phoenicia Specialty Food Downtown Market on Thursday, February 11, 2016. The Precinct2gether bus departs from the Freeman Library parking lot no later than 9:30 AM.
Freeman children can start off the new year by attending a fun program this month. On Mondays, we continue with Maker Monday programs for children 5-12 years old at 4:30 pm. These weekly afterschool programs feature an activity or a craft. On Thursday January 28, children 5-12 years old can help us get ready for Mardi Gras by decorating a shoebox float at 4:30 pm. Tickets are required for these programs. They are free and given out 30 minutes before the program.
Last year, local teen Karan Jerath made use of the Innovation Lab to 3D print a model he designed to address the remediation of deep-water oil spills. We are happy to report that Karan went on to win the Young Scientist Award and a sizeable cash prize at Intel's International Science and Engineering Fair 2015. Not only that, Karan recently made Forbes magazine's 30 Under 30 List for the Energy Sector. You can see a photo and description of him on the Forbes website with the model he printed right here in the Lab. Way to go, Karan!
The Jocelyn H. Lee Innovation Lab is available for you to turn your ideas into realities. What would you like to make?
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If your looking for a great accommodation outside of downtown this is it! Beautiful grounds, amazing trail running and mountain biking right out your door. Arrived and was given a free upgrade upon check in, didn't even need to ask. Amazing views from the pool. Kids loved it. The best part, the resort gives you a free bus pass to get bak and forth to and from downtown. The bus picks you up right at the resort, used this all week!
- Official Description (provided by the hotel):
- Tucked away on Tunnel Mountain, Hidden Ridge Resort is quiet and secluded with some of the most spectacular views in Banff and the Canadian Rockies. The modern condos feature wood burning fireplaces, full kitchens and patios or balconies. Take a stroll along one of the many hiking trails around Tunnel Mountain that start outside your door. The tranquil and secluded setting makes it one of Banff's best-kept secrets. Only a mile from downtown area. ... more less
- Reservation Options:
- TripAdvisor is proud to partner with Expedia, Orbitz, Priceline, Hotwire, TripOnline SA, Travelocity, Hotels.com, Booking.com and Cheap Tickets so you can book your Hidden Ridge Resort reservations with confidence. We help millions of travelers each month to find the perfect hotel for both vacation and business trips, always with the best discounts and special offers.
- Also Known As:
- Hidden Ridge Hotel Banff
- Hidden Ridge Resort Banff
- Hidden Ridge Banff


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Even though we ARE Nikon lovers,we are NOT affiliated with Nikon Corp. in any way.
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2820 posts
"RE: D400 Announced"
>I'm a amatuer sports photographer and want video, and want to>properly supplement my D200. My D70sw is going to my daughter>and replace it with upgrade body, like my D200, or a D300 or>the D5100, but don't want to spend over $1,000. I want the>video feature, especially the ability to shoot short HD clips>to accompany my slide shows. I own a Nikon AF 70-200 VR F2.8,>and a new Sigma AF 18-50 F2.8. Recommendations?>Bob>Bob,You will need to get a separate microphone or use a portable digital recorder when using your 70-200mm in VR mode. The D300s built-in mic easily picks up the sound of the VR motor.Here is my Rode stereo video mic:Ian
If only Mozart had had a camera


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|Message view
|« Date » · « Thread »
|« Date » · « Thread »
|"Bill Barker" <wbar...@wilshire.com>
|RE: svn commit: r371765 - /tomcat/container/tc5.5.x/catalina/src/share/org/apache/catalina/connector/Response.java
|Tue, 24 Jan 2006 01:55:01 GMT
> -----Original Message----- > From: firstname.lastname@example.com [mailto:firstname.lastname@example.com] > Sent: Monday, January 23, 2006 5:13 PM > To: email@example.com > Subject: svn commit: r371765 - > /tomcat/container/tc5.5.x/catalina/src/share/org/apache/catali > na/connector/Response.java > > Author: remm > Date: Mon Jan 23 17:13:19 2006 > New Revision: 371765 > > URL: http://svn.apache.org/viewcvs?rev=371765&view=rev > Log: > - Remove nonsensical systematic inclusion on ISO-8859-1 > charset in the content type, which is noth > useless and inefficient. > -1 Sending the charset used by the Writer is very clearly required by the servlet spec. This message is intended only for the use of the person(s) listed above as the intended recipient(s), and may contain information that is PRIVILEGED and CONFIDENTIAL. If you are not an intended recipient, you may not read, copy, or distribute this message or any attachment. If you received this communication in error, please notify us immediately by e-mail and then delete all copies of this message and any attachments. In addition you should be aware that ordinary (unencrypted) e-mail sent through the Internet is not secure. Do not send confidential or sensitive information, such as social security numbers, account numbers, personal identification numbers and passwords, to us via ordinary (unencrypted) e-mail. --------------------------------------------------------------------- To unsubscribe, e-mail: firstname.lastname@example.com For additional commands, e-mail: firstname.lastname@example.com
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Closed right on an average Fib. retracement number ( between 1st and 2nd level Fib. retracement) add that to the volume = Fund accumulation. Tomorrows Day Traders will pay more to get back in. Based upon my model from low to impulse high. For those that know or remember me I use a combination of E Wave and Fib. numbers. Looks very positive. I will be prepared to buy any gap down open tomorrow as I believe funds will do the same. Finally a very nice day and I think more to come we have Cats and data coming soon. Mo Mo should continue.
giggle giggle ..Kvncmcdd- you know some actually know what Fibonacci is and the Elliot waves are all about...
one time I went to see R Prechter and guess who his guest was!! Tony Robbins! who lives right down the street from me! LOL giggle giggle....
Delusional much?
Legit! The men are in and the boys aka the Terry's and family are out.
Sentiment: Strong Buy


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ELI-ASH wrote:
Neeeko wrote:
Neeeko wrote:
ELI-ASH wrote:
Neeeko wrote:
ELI-ASH wrote:
Neeeko wrote:
looking for kidde or astro furniture
Hello again XD, I have the full astro but its gonna take a little while since i gotta order everything. What Astro items do you currently own?
Lol all i have is the dresser, nothing else
OK for the:Astro bed,Astro CD Player,Astro Chair,Astro Clock,Astro Closet,Astro Lamp,Astro Shelf,Astro Sofa,Astro Table,Astro TV,Astro Wall,Astro Floor I can do 170k. and because of our previously deal that also means you get both bro staches now XD.
Alright sounds good =) Thank you=D tell me whenever your ready and add me=))
And that comes to a total of 380k right? for both sets
Thats correct,I added you back.
Alright great =)
3ds Friend code 5343-8418-9364
Nintendo Network ID: Nekokanane


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I am trying to compile imapfilter 2.4.1 ( https://github.com/lefcha/imapfilter ) in CentOS 5.6. I believe I've got all the dependencies sorted but when I run make I get:
make[1]: Entering directory `/home/src/imapfilter-2.4.1/src'
cc -Wall -O -DMAKEFILE_SHAREDIR='"/usr/local/share/imapfilter"' -c -o core.o core.c
core.c:41: error: expected '=', ',', ';', 'asm' or '__attribute__' before 'ifcorelib'
core.c: In function 'ifcore_append':
core.c:947: warning: implicit declaration of function 'lua_strlen'
core.c: In function 'luaopen_ifcore':
core.c:1162: warning: implicit declaration of function 'luaL_register'
core.c:1162: error: 'ifcorelib' undeclared (first use in this function)
core.c:1162: error: (Each undeclared identifier is reported only once
core.c:1162: error: for each function it appears in.)
make[1]: *** [core.o] Error 1
make[1]: Leaving directory `/home/src/imapfilter-2.4.1/src'
make: *** [all] Error 2
Based on other user comments and file revision dates I am sure this should compile. I am guessing I'm missing a library somewhere. I'll appreciate any help I can get on this.


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I've been praised for my ability to give great back massages, making people laugh, turning the worst days into something special, and so much more.
Though i may sound generic, I am far from it. My goofiness conquers all. If you don't believe me, send me a message and see for yourself.
and that I look awfully familiar...like they've seen me in a movie before
I look like a rock star (sadly im not one in real life...jus in the privacy of my own home where i jam on my guitar without any p...ive said too much -_- )
TV Series: Titus, Firefly, Arrested Development, Breaking Bad, and anything that hits me right in the nostalgic-gut (ie: cartoons, cheesy 90s movies, etc)
Bush, Killswitch Engage, Metallica, Three Days Grace, Barenaked Ladies, Foo Fighters, Soundgarden, Breaking Benjamin, Dethklok...pretty much anything but most country and rap (note: old school hip hop gets a pass)
Hitchhiker's Guide to the Galaxy, A Separate Peace, Star Wars: Shadows of the Empire, Akira, and various graphic novels...not a big reader but I dabble every now and again
my computer/the net (kinda how I run my business)
my 2 goofy dogs, Baxter and Xena
Breakfast (most important meal of the day)
Cold Weather (f*ck this heat)
Where I'll be in 500 years
Where my money's going
If you choked a smurf, what color it would turn?
If one synchronized swimmer sinks...do they all sink?
bwahahahaha just kidding
but im on my way, so just stay where you are..wait..where are you going?!
you're a nerd/geek
you love big dogs
you're honest
you have your own car AND know how to drive it.
you can make me laugh
you'd like to send me a compliment
Youre my soul mate
You work for publishers clearinghouse and have a large check to present to me


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Convert-It is a multimedia and conversion software suite for Windows based PCs. It allows you to play, convert, access, and burn videos, DVDs, images, documents and audio. With Convert-It you pay one low price and get access to all 7 products in the suite. The suite ... application providing easy, stable and fast CD copying to WMA, MP3, MP4, WAV, OGG, and FLAC audio .... Free download of Convert It 1.2
When you want to watch your favorite DVD movies on PlayStation smoothly then you need to convert DVD to PlayStation supported video files. For this conversion, you can use DVD to PS Vita converter software which can convert DVD disc/movies to PS Vita easily. Using this software, you can burn videos and copy DVD directly to DVD discs. It converts any 2D .... Free download of DVD to PS Vita Converter 3.0.0
If you want to see any DVD video on your Nintendo DS device then you ... this task by applying this efficient and fast DVD to DPG video converter. Free download DVD to Nintendo DS video converter and enjoy your favorite DVD movies in to your Nintendo device. This tool can convert DVD .... Free download of DVD to DPG Converter 1.0
Powerful 3GP video converter and 3GP video editing software for creating 3GP videos. With 3GP Video Converter Factory Pro, you can convert any video format to 3GP/3G2 and play it on you mobile phone, such as Nokia, BlackBerry, Palm, Sony Ericsson, Motorola, Samsung, Philips, LG, NEC, etc. 3GP Video Converter Factory Pro also an excellent and .... Free download of 3GP Video Converter Factory Pro 2.0
Convert MP4 to Any is an all-in-one MP4 Converter. It can convert MP4 to JPG, PNG, GIF, DivX, XviD, AVI, VCD, DVD, SVCD, MPEG, VOB, FLV, SWF, HD Video, 3GP, 3G2, QT, MOV, WMV7, WMV8, WMV9, ASF. It can rip MP4 audio to AAC, AC3, AU, WAV, MP3, AIFF, FLAC, OGG, .... Free download of Convert MP4 to Any 1.0.3
This software offers a solution to users who want to convert one or more AVI video files into 3GP format. The user simply chooses the file/s or an entire folder to be processed before starting the conversion. Using this .... Free download of Convert Multiple AVI Files To 3GP Files Software 7.0
This software offers a solution to users who want to convert one or more 3GP video files into AVI format. The user simply chooses the file/s or an entire folder to be processed before starting the conversion. Using this .... Free download of 3GP To AVI Converter Software 7.0
To FLAC Converter Free for Mac easily rips CDs and converts media files to high-quality FLAC format. To FLAC Converter converts most of video and audio input types of ... AIFF, FLV, WAV, MPG, ASF, MPEG, MPE, MOV, 3GP, M4V, MKV, MOD, OGM, DV, VID and others. ... and volume normalizer ensure quick and productive conversion to FLAC. Find out more at amvidia.com/to-flac-converter. .... Free download of To FLAC Converter Free for Mac 1.0.9
This software offers a solution to users who want to convert many M4As to MP3s. Many songs purchased from iTunes are in M4A format which makes them difficult to play with MP3-only devices. This software solves this type of problem by converting those M4A files in batch. Simply drag and drop the files you would like to work with and click the 'Start' button to .... Free download of Convert Multiple M4A Files To MP3 Files Software 7.0
DVD Copy Ultimate is an ultimate DVD solution for copying DVD and ripping DVD. As a DVD copier, Any DVD Cloner Platinum can copy DVD movie to DVD and copy DVD to hard drive with 1:1 ratio in a super high DVD copy speed, shrink DVD9 to DVD5 with best quality, copy DVD to hard .... Free download of DVD Copy Ultimate 1.1.7


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The Thurston County Planning Commission will hold a public hearing Wednesday, August 17, 2016, on proposed changes to development codes for the Urban Growth Areas of Lacey, Tumwater, and Olympia, including changes related to low impact development (LID). The hearing will be held at 7 pm in room 152 in the County Courthouse Building 1 at 2000 Lakeridge Dr SW in Olympia, WA 98502.
See the proposed 2016-2017 Development Code amendments.
Welcome to the Thurston County Long Range Planning Division. The mission of Long Range Planning is to plan for sustainable land use and development within the unincorporated areas of the county so communities can thrive in a healthy environment.
We are pleased to provide information about our past and current projects, and hope that it helps you understand and participate in the long-range planning process. If you have questions about permitting or building applications, please visit the Permitting Program (external link).
Connect with us on
Also, be sure to visit the Planning Commission website for meetings and agendas.


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Bruce Dickinson has revealed that Reading and Leeds are very important shows for him as Reading was the first festival he went to as a kid, and he was originally asked to join Maiden when he was there!
Iron Maiden headline Leeds tonight at 9.10pm at Bramham Park, before closing Reading on Sunday night. The singer confided to The Sun, "It will be a big one…we'll be nervous."
Stay posted as we bring you coverage from both sites throughout the weekend.


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Samsung starts production of 4Gb LPDDR3 modules for smartphones and tablets
Will ramp up DRAM production on a 20nm process node this year
CHIPMAKER Samsung announced that it has started to produce 4Gb LPDDR3 DRAM modules using a 20nm class process node.
Samsung's market leading position in the DRAM market has been unchallenged for years, but with Micron trying to complete its purchase of Elpida and Hynix working with chip vendors on GDDR, the firm is pushing ahead with its low-power DDR memory research. Samsung announced that it has put 4Gb LPDDR3 DRAM modules into production on a 20nm class process node.
Samsung said that its LPDDR3 modules that are intended to be used in smartphones and tablets will run at 2.13Gbit/s. However the firm is relying on more than just performance to shift its new modules, saying that four of its 4Gb LPDDR3 modules can be used to create a 2GB package with a height of 0.8mm.
Young-Hyun Jun, EVP of memory sales and marketing at Samsung Electronics said, "By providing the most efficient next-generation mobile memory with a very large data capacity, we are now enabling OEMs to introduce even more innovative designs in the marketplace.
"Our 20nm-class four gigabit mobile DRAM provides another example of our ability to deliver well-differentiated, high-performance, high-density memory to customers in a timely manner."
Although DRAM makers such as Samsung have been hurting as the PC industry's use of mature DDR3 modules declined and waning demand kept prices low, low-power smartphones and tablets represent a growing market with new technology that commands a price premium.
Samsung added that it plans to ramp up production of DRAM on its 20nm class process node later in the year, putting further pressure on Hynix and Micron. µ
INQ Latest
Silicon chip breakthrough promises genuinely smart devices
Next-gen devices enabled by integrating novel materials on silicon
Google Updates: $99 laptop, data centre efficiency boost, Chrome 52
Plus there's a new way to read comics in town
6 of the best PC games of 2016 so far
Find out which six games have most impressed us so far this year
iPhone 7 release date, specs, price and rumours
Video shows off upcoming handset in Rose Gold compared to iPhone 6S predecessor


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Welcome to Opera on Tap DC Metro
Opera on Tap is a non-profit organization whose mission is to break down the stereo-type that opera is a stuffy or elitist art form by bringing it to bars. Local singers let their hair down and bring you into what feels like an after hours back stage party, singing some of opera's best known and little known pieces in a friendly, relaxed atmosphere.Contact us with any questions at firstname.lastname@example.com
Opera at Vendetta
#SingersChoice at The Pinch
Opera at The Wonderland Ballroom
Its getting hot out there!!!
Join us down the Rabbit Hole for #operainbars
Saturday, July 23rd at The Wonderland Ballroom from 7-9pm
Artists: Mandy Brown, Ben Clark, Elizabeth Mondragon, Carla Rountree, and David E. Chàvez on piano.
Opera on Tap T-shirts have arrived!!!!!!
We will be selling Opera on Tap – Opera Stirred t-shirts at our shows.
RED, GREEN and BLACK in both Unisex and Women's fits. $20-$25 each


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Chihuahua Merlin
Age: 10 months
Sex: neutered male
Size: 5 pounds
Merlin's story: Magical Merlin was discarded at a shelter with his whole head and parts of his body burned. Despite this terrible abuse, he is a friendly, outgoing little guy. He has a beautiful blue coat with white patches on his chin, chest and feet. This pocket pooch will be the life of your party, just like he is in his foster home.
Adoption fee: $250, includes registered microchip, neuter, vaccines, worm treatment
Adoption procedure: Please complete an adoption application online at lovebugsrescue.org/.
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The Lakes at Brookside offers close-knit hometown living with Lakes, amenities & large yards right next to vibrant Vint Hill. From the $400s
Earn Miles and MQMs with Miles Boost™. Learn More. Terms Apply.
All our programs are 100% online pick your program and design your course schedule around your life.
Earn your degree online through Walden's CCNE-accredited nursing program and make a difference in your patients' lives. Request free info today!
Try our one-step facial cleanser for the ultimate clean or our cleansing wipes for Purity on the go! Natural oil extracts condition and refresh skin.
The 2015 Dodge Challenger Classic design meets powerful performance. Meet the Dodge Challenger. Your day just got a lot more interesting.


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Pfeiffer Beach
Pfeiffer Big Sur State Park
Named after Big Sur's first European settlers who arrived in 1869, this is Big Sur's largest state park, where hiking trails loop...
Andrew Molera State Park
Named after the farmer who first planted artichokes in California, this oft-overlooked park is a trail-laced pastiche of grassy meadows,...
Big Sur Discovery Center
From the parking lot at Andrew Molera State Park, walk south to this educational nature center to learn all about the endangered...
Maiden Publick House
Just south of the Big Sur River Inn, this dive has an encyclopedic beer bible and motley local musicians jamming, mostly on weekends.
Big Sur Roadhouse
This modern roadhouse glows with color-splashed artwork and an outdoor fire pit. At riverside tables, fork into upscale...
end of Sycamore Canyon Rd · interesting places nearby
Pfeiffer Beach information
This phenomenal, crescent-shaped and dog-friendly beach is known for its huge double rock formation, through which waves crash with life-affirming power. It's often windy, and the surf is too dangerous for swimming. But dig down into the wet sand – it's purple! That's because manganese garnet washes down from the craggy hillsides above. To get here from Hwy 1, make a sharp right onto Sycamore Canyon Rd, marked by a small yellow sign that says 'narrow road' at the top.
From the turnoff, which is a half-mile south of Big Sur Station on the ocean side of Hwy 1, it's two narrow, twisting miles down to the beach (RVs and trailers prohibited).